Mixtures of novel conjugated polyoxyethylene-polyoxypropylene compounds



United States Patent 3,036,118 MIXTURES OF NOVEL CONJUGATED POLY-OXYETHYLENE-POLYOXYPROPYLENE COM- PDUNDS Donald R. Jackson, Wyandotte,and Lester G. Lundsted, Grosse Ile, Mich, assignors to WyandotteChemicals Corporation, Wyandotte, Mich, a corporation of Michan loDrawing. Filed Sept. 11, 1957, Ser. No. 683,227 14 Claims. (Cl. 260-484)This invention relates to mixtures of novel conjugated polyoxyethylenepolyoxypropylene compounds. In a more specific aspect, this inventionrelates to new nonionic surface active agents and a method for preparingsame wherein the new surface active agents are essentially mixtures ofconjugated or block polymers of ethylene oxide and propylene oxide.

This application is a continuation-in-part of our application Serial No.365,244, filed June 30, 1953, now abandoned.

Nonionic surface active agents composed of a waterinsoluble orhydrophobic nucleus, such as a long hydrocarbon chain or analkyl-substituted ring compound, e.g. nonylphenol, and awater-solubilizing polyoxyethylene chain are well known in the art. Suchsurface active agents have excellent properties for many uses, but adisadvantage in this class of materials lies in the inflexibility of thewater-insoluble or hydrophobic portion of the molecule. Any alterationin properties attributable to the hydrophobic portion of the surfactantcan only be accomplished by selecting a completely different waterinsoluble compound with which to condense ethylene oxide. Frequentlyhowever, different uses of surfactants require varying surfactantproperties which differ only in small increments for the bestperformance.

An important contribution to the art in this regard is represented bythe disclosure of L. G. Lundsted in US. 2,674,619, issued on April 6,1954. Lundsted disclosed new surfactant compositions which areexemplified by the mixtures obtained by sequentially condensingpropylene oxide with a lower molecular weight reactive hydrogencompound, such as propylene glycol, to produce a waterinsoluble,hydrophobic polyoxypropylene polyol, and then condensing ethylene oxidewith the polyoxypropylene polyol in an amount sufiicient to solubilizethe polyoxypropylene polyol and provide surface active properties. Withthe benefit of Lundsteds disclosure, the art can obtain surface activeagents with properties which can be widely varied since both thehydrophobic and hydrophilic portions of the molecule can be altered bysimply controlling the amounts of propylene oxide and ethylene oxideused in preparing the compounds. The compositions disclosed by Lundstedhave opened the door for applications of nonionic surfactants derivedfrom alkylene oxides in uncounted ways because of the new flexibility inchemical and physical properties that has been afforded.

Room for further improvement still exists, however. Even with theflexibility of chemical and physical properties afiorded by thecompositions of Lundsted wherein propylene oxide is initially condensedwith a low molecular weight reactive hydrogen compound, and ethyleneoxide in a solubilizing amount is then condensed therewith, we havefound that specific combinations of properties desirable in a surfactantcould not be attained in the compositions of Lundsted. Keeping in mindthe extremely wide variety of uses of nonionic surface active agents, itcan well be appreciated that new uses are enpropylene polyol.

3,036,118 Patented May 22, 1962 ethylene oxide and propylene oxide whichhave new combination of surface active properties.

A still further object is to provide a new method for preparing surfaceactive agents derived essentially from ethylene oxide and propyleneoxide.

As was stated above, the surface active agents disclosed by Lundsted areprepared by initially condensing propylene oxide with a low molecularweight reactive hydrogen compound, such as propylene glycol, so as toproduce a hydrophobic polyoxypropylene polyol, and then condensingethylene oxide with the hydrophobic polyoxy- We have discovered,however, that a completely new series of surface active agents, from theviewpoint of chemical and physical properties, can be obtained byreversing the order in which propylene oxide and ethylene oxide areemployed in the compositions of Lundsted. Surprisingly, it has beenfound that when exactly the same amounts of propylene oxide and ethyleneoxide are employed in preparing the compositions of Lundsted and inpreparing the compositions of this invention where the order ofcondensation of propylene oxide and ethylene oxide is reversed, thesurface active properties obtained in the compositions of this inventionare completely different. In general, we have found that the cloud pointand foam height of the compositions of this invention are significantlylower than the cloud point and foam height of the Lundsted compositionswhen comparisons are made between compositions prepared with the sameweight of the same materials but differing in the order in which thepropylene oxide and ethylene oxide are condensed. Detergency tests ofthe two classes of surfactants show varying results, but in every casethe detergency of the composition of this invention is significantlydifferent from the detergency of the strictly comparable composition ofLundsted.

Thus, it will be readily appreciated that a further advance in thesurface active agent art is represented by the compositions of thisinvention since flexibility in chemical and physical properties isincreased. Frequently, success or failure in the use of any particularsurface active agent depends on the presence of a precise balance ofsurface active properties in the surfactant. The range of propertiesthat can be obtained in the surfactants of Lundsted based on blocks ofoxypropylene and oxyethylene chains has been significantly expanded bythe present invention wherein the order of condensation of propyleneoxide and ethylene oxide has been reversed.

Before discussing the new compositions and method of this invention indetail, it would be well to amplify the terms mixtures, conjugated andblock as used in this specification and in the appended claims todescribe the compositions of the invention. It is well recognized in thefield of alkylene oxide chemistry that when one subjects a reactivehydrogen compound to oxyalkylation, such as oxyethylation oroxypropylation, what is actually produced is a polymer of the alkyleneoxide except for the terminal group. Furthermore, where the amount ofthe -provided by the starting material.

ailrylene oxide employed is relatively large, one does not and claims,there is meant the average theoretical molecular weight which equals thetotal of the grams of propylene oxide employed per mol ofoxyethylene-reactive hydrogen compound condensate. 'rnaterials givenherein according to the Lundsted patent,

In the examples of the theoretical molecular weight of the 'oxypropylenechain equals the total grams of propylene oxide per mol of reactivehydrogen compound.

The compositions of Lundsted and of this invention are such mixtureswhich are further defined as being conjugated or block polymers ofalkylene oxides. Thus, compositions derived by condensing simultaneouslyabout equal parts of ethylene oxide and propylene oxide, such as thelubricant compositions disclosed in Toussaint et al., U.S. 2,425,846,are distinguished since in the latter case a heteric oxyethyleneoxypropylene chain is obtained wherein the different oxyalkylene groupsare distributed random- 1y throughout the oxyalkylene chain. On theother hand, the compositions of this invention contain a block ofoxyalkyle'ne groups in a chain connected to a block of differentoxyalkylene groups in a chain thus providing the conjugated or repeatedunit structure which is necessary for hydrophobic md hydrophilicproperties. noted hereinabove, the starting material for preparing thecompositions of the invention is a low molecular weight reactivehydrogen compound. This fact is of the utmost importance indistinguishing the compositions of the invention from surface activeagents of the prior art wherein alkylene oxides have'been employed forvarious purposes. Lundsted was the first to disclose surface activecompositions wherein the hydrophobic element derived its hydrophobicproperties strictly from a defined'oxypropylene chain. Compositions ofthe prior art wherein ethylene oxide is condensed with an initiallywater-insoluble, relatively high molecular weight and hydrophobicreactive hydrogen compound, or even where propylene oxide is initiallycondensed with such a starting material followed by 'oxyethylation,obviously cannot derive the hydrophobic characteristic necessary in'a'surface active agehtfrom an oxyalkylene' chain since such acharacteristic is already For example, U.S. 2,552,532 discloses a seriesof compositions obtained by condensing, initially, ethylene oxide and,subsequently,

propylene oxide with polypentaerythritols, such as tri-,

tetra-, pentaand'higher pent-aerythritols. We have found 'thatthe lowestmember of the series, tripentaerythritol, is

V sufficiently hydrophobic in itself so that a surfactant is obtained bymerely condensing ethylene oxide therewith.

The higher members of the series are even more hydrophobic and so suchcompositions ar'ecomparable to other alkylene oxidecondensate-surfactants of the prior art wherein a hydrocarbon radicalsupplies the hydrophobic characteristic for the surfactant and not theproperly defined oxypropyle'rie chains set forth in the compositions ofthis invention} so also in the compositionsof this invention, thehydrophobic characteristic is directly attributable to the definedoxypropylene chains ja'nd the reactive hydrogen compound employed mustnot be suhiciently "hydrophobic: in itself so that a 'surfactantcould beob-t taine'd merely :by condensing a solubilizing. amount of amyl se'oxidettherewith, new use; t pe or reactive hydrogen compound werense'd,flexibility of properties As has been i would be largely lost since thehydrophobic character istic of the surfactant would be dominated by thestarting material.

It will be noted that the starting material-reactive hydrogen compoundgenerally has very little effect on the properties of the compositionsof the invention, since by definition, the reactive hydrogen compoundcannot be one which contributes significantly to the hydrophobiccharacteristic of the composition. This is true in spite of the factthat a major distinction from the prior art in the compositions of theinvention lies in the fact that at hereindefined reactive hydrogencompound is employed as discussed above. The reactive hydrogen compoundused in preparing the compositions of this invention and in carrying outthe method of the invention must fulfill two conditions, initially: (1)Its reactive hydrogen atoms must be sufficiently labile to open theepoxide ring of ethylene oxide; and, (2) The reactive hydrogen compoundmust react with methyl magnesium iodide to liberate methane in theclassical Zerewitinoff reaction (see Niederl and Niederl, Micromethodsof Quantitative Organic Analysis, page '263, John Wiley & Sons, New YorkCity, 1946) Furthermore, as stated hereinabove, the reactive hydrogencompound must be a relatively low molecular weight, water-solublecompound, such' as one having up to about 6 carbon atoms, and musthave'at least 2, and preferably not more than about 6, reactive hydrogenatoms. It will be recognized, however, that a fairly broad range ofreactive hydrogen compounds falls within this definition.

Thus, the lower molecular weight, aliphatic, polyhydric alcoholsconstitute one class of reactive hydrogen compounds that is especiallyuseful in preparing the compositions of this invention. Such alcoholscan have from about 2 to 6, inclusive, carbon atoms per molecule, andexamples of these materials are ethylene glycol, propylene glycol,2,3-butylene glycol, 1,3-butylene glycol, -1,5-pentanediol,1,6-hexanediol, glycerol, trimethylolpropane, sorbitol, sucrose and thelike. Another class of reactive hydrogen compounds that can be used isthe alkylamines and alkylene polyamines having at least 2 reactivehydrogen atoms, such as methylamine, ethylamine, propylamine,butylamine, hexylamine, ethylenediamine, 1,6-hexanedi amine,diethylenetriamine, and the like. Also, such cyclic amines aspiperazine, Z-methylpiperazine and 2,5- dimethylpiperazine can also beused. Amides constitute a further class of such reactive hydrogencompounds, such as acetamide, succcinamide and benzenesulfonarnidet Astill further class of such reactive hydrogen compounds is the diandpolycarboxylic acids,'such as adipic acid, succinic acid, glutaric acid,aconitic acid, diglycollic acid, and the like. It will be recognizedthat the --reactive hydrogen'compound can be one containing diiferentfunctional groups having reactive hydrogen atoms, also, such as citricacid, glycollic acid, ethanolarnine, and the like. Still other suchreactive hydrogen compounds can also be used so long as the particularcompound meets the requirement set forth, i.e., relatively low molecularweight, reactivity with ethylene oxide and at least 2 reactive hydrogenatoms.

The compositions of'this invention are prepared by condensing a suitablereactive hydrogen compound with a defined weight of ethylene oxide toproduce a polyoxyethylene polyol '(within which we include the reactivehydogen compound) and subsequently condensing the ide so that theoxypropylene chains in the product mixtu're have a defined averagemolecular: weight.

Since the reactive hydrogen compound'employed has at least 2 reactivehydrogen. atoms, the initially produced polyoxyethyleneipolyolcorresponds to the structure,

' tt zt ionnn wherein R is the nucleus of the reactive hydrogencompound, x is the number of oxyethylene chains attached to the reactivehydrogen compound nucleus at the sites of the reactive hydrogen atoms,and n has a value such that the weight of oxyethylene groups constitutesfrom about to 90 weight percent of the final oxyethyleneoxypropylenecomposition. Thus, where ethylene glycol is the chosen reactive hydrogencompound, the structure of the initially produced polyoxyethylene polyolis simply wherein a-l-b is equal to n defined above.

Where the reactive hydrogen compound chosen is ethylenediamine, theinitially produced polyoxyethylene polyol has the structure,

wherein a-I-a'+b+b' is equal to n defined above.

The final composition of the invention is produced by condensingpropylene oxide with the polyoxyethylene polyol described above, and asufiicient quantity of propylene oxide is employed so that the molecularweight of each oxypropylene chain which is formed is at least 900. Thelower limit on the molecular weight of the oxypropylene chains issignificant in that at a molecular weight of about 900 an oxypropylenechain changes from essentially hydrophilic at lower molecular weights tohydrophobic at about 900 and higher molecular weights. This isdemonstrated by the data and drawings in the Lundsted patent,particularly FIGURE 1, therein. Since 40 each oxyethylene chain in thepolyoxyethylene polyol contains a hydroxyl radical on its terminalcarbon atom, the compositions of the invention have an oxypropylenechain attached to each oxyethylene chain, thus providing the conjugatedor repeated unit or block polymer type of structure to which we referredearlier. The molecular weight of the oxypropylene chains can be up toabout 25,000 or more and useful surfactant compositions of thisinvention are obtained throughout this range.

Thus, the structure of a composition of this invention corresponds tothe formula wherein m has a value such that the oxypropylene chain has amolecular weight of at least about 900, such as about 900 to 25,000, andwherein n and x have the significance ascribed to them hereinabove.Where the reactive hydrogen compound employed is ethylene glycol, thecomposition of the invention has the structure,

momo'uhommnowherein a+b equals n which is a value such that the weightof the oxyethylene chains constitutes about 20 to 90 weight percent ofthe total composition, and m is a value such that the average molecularweight of each oxypropylene chain is at least about 900 to 25,000.

d The compositions of this invention have the most desirable combinationof properties for use as detergents when the oxyethylene chainsconstitute about to 75 weight percent of the total compositions andwherein the 5' molecular weight of the oxypropylene chains is about 1500to 15,000, and compositions falling within these limications arepreferred by us for many uses.

Our invention set forth herein can also be stated in terms of the newmethod by which the compositions of the invention are prepared. Theconditions and catalyst employed are those conventionally employed inalkylene oxide condensation reactions. However, our method whichcomprises condensing ethylene oxide with a relatively low molecularweight reactive hydrogen compound 5 containing at least 2 reactivehydrogen atoms to form a.

polyoxyethylene polyol and thereafter condensing propylene oxide withsaid polyoxyethylene polyol, the amount of ethylene oxide employed beingsufiicient so that the polyoxyethylene polyol constitutes about 20 to 90weight 20 percent of the final composition and the amount of propyleneoxide employed being sufi'icient so that the oxypropylene chains have anaverage molecular weight of about 900 to 25,000, is believed to expressour invention in terms of the method steps employed.

As has been stated, the actual conditions employed in carrying out thealkylene oxide condensation reactions which are necessary in order toobtain the compositions and to carry out the method of the invention arewell known in the art. The disclosure of Lundsted in US. 2,674,619,columns 4 and 5, sets these conditions forth and this disclosure incombination with the disclosure in our examples to follow describes thealkylene oxide reactions adequately. The compositions of this inventionare particularly useful as detergents and tests which we have -made onthe compositions of the invention to show their usefulness as detergentsinclude the Carbon Soil Removal Test described in U.S. 2,674,619, column6', lines l8-75,

and column 7, lines 1-49. The result of this test is a Carbon SoilRemoval value taken at either 90 F. or

140 F. for the test composition which expresses its detergency in termsof its percentage efiectiveness when' compared to the standard 0.25%solution of sodium kerylbenzenesulfonate described in the test procedurereferred to above. Other tests which we have made relate to the cloudpoint of the compositions and the foam height produced by thecompositions under controlled conditions.

The cloud point test is carried out by heating a 10 weight percentsolution of the test composition in distilled water in a test tubeplaced in a water bath. The water bath is gradually heated at a rate ofabout one degree a minute and so that the bath temperature is not morethan 5-10 degrees centrigrade higher than the test solution particularlynear the cloud point. The test solution is agitated by a low-speedpropeller-type stirrer and the cloud point observation of the testsolution is made against a dark background. The cloud point is taken asthe temperature at which definite milky striations or minute butdiscrete particles of a separate phase are observed.

The foam height test is carried out by placing 10 liters of a 0.10weight percent solution of the test composition in tap water in a Pyrexglass jar measuring 10 in diameter and 10" in height. The Pyrex jar isequipped with a propeller-type stirrer, knife blade heaters, athermoregulator and a thermometer. A small, centrifugal pump is arrangedto circulate the solution in the jar through a calibrated glass flowmeter to a jet orifice prepared from the 70 base of a No. 20 Becton,Dickinson and Company bypodermic needle by enlarging the hole in thebase with a No. 56 twist drill. The jet orifice is mounted coaxiallyinside a Pyrex glass tube (51 mm. by 910 mm.) which is placed verticallyin the solution. The jet is arranged so that it is 600 mm. abovethe-surface of the'solution test. The jet is then arranged so as to passthe solution have entirely different combinations of these three V 7 in.the jar, and the Pyrex glass tube is arranged so as to project 210 mm.below the surface of the solution. The test solution is heated to andmaintained at 120 F. The centrifugal pump is started and a flow rate of200400 rrl. per minute of the solution is metered through the jet. Theflow is adjusted by lay-passing part of the solution stream back intothe jar before passage through the flow meter. The solution passingthrough the jet is directed against the wall of the vertical tube Whilethe flow is adjusted and while the temperature is brought to equilibriumin order to prevent foaming prior to the actual coaxially downwardthrough the tube without touching the tube walls to impinge upon thesurface of the solution located in the Pyrex tube. Time is measured fromthe instant the solution impinges on the liquid surface and theresulting.foamis'measured at the end of 10 minutes. The

foarn height readings are obtained from a calibration on the outside ofthe Pyrex tube with the'zero' mark at the surface of the solution andare expressed in millimeters. We have found that the compositions ofthis invention detergency properties, carbon soil removal value, cloudpoint and foam height, than the compositions of the Lundsted patent.Generally, the compositions of this invention have significantly lowercloud points and foam heights and these trends in combination with thedistinctly different carbon soil removal values make our composi tions adefinite advance in the'art since flexibility inproperties. ofsurfactants based on alkylene oxide block polymers is increased. Thesefacts will. become apparent from the examples which follow andparticularly the'direct comparisons of the properties of thecompositions of the invention and the compositions of the Lunstedpatent. The examples are supplied in order to exemplify the compositionsand method of the invention andshould not be employed to unduly limitthe scope of our invention when due regard is given to the descriptiongiven hereinaabove and to follow.

EXAMPLES.

' cordance with this invention. The procedurewhich excatalyst for thesecond and subsequent stages. those runs, where N-methylmorpholine orwater was used 8: emplifies the method of this invention was generallythe same throughout although variations in operating conditions andequipment were made to a certain extent in order to expedite thereactions and because of volume limitations dictated by the reactorsemployed.

The reactors employed were a one gallon, stainless steel autoclaveequipped with a stirrer, thermocouple, pressure gage and reactant inlettube whose outlet. was directly under the stirrer; and, in some cases, a3-necked glass flask equipped with a stirrer, condenser, thermometer andalkylene oxide inlet tube. The exact conditions, materials and weightsof materials used are summarized in Table I below. In general, thereactive hydrogen compound and catalyst were initially charged into thereactor. The amount of catalyst charged to the reactor at the start ofeach stage is indicated in Table I and a dash means that no additionalcatalyst was used. In the'runs where N-methylmorpholine or water wasused as a solventcatalyst, the reactor was washed and dried followingremoval of the first stage product before charging KOI-l Also, in

in the first stage, the product of the first stage was stripped at 100C. and about 4 mm. Hg pressure for 1 hour before charging a portion ofthis product to the second stage.

Ethylene oxide was then admitted to the reactor while maintaining areaction temperature in the range of 135 C. and average pressure of 1-95p.s.i.g. The total reaction time varied from about 2-11 hours. of volumelimitations imposed by the reactors, the polyoxyethylene polyol was madein stages, taking the indicated amount of the product of the firststage, charging it back into the reactor for further reaction withethylene oxide as indicated. When the polyoxyethylene polyol having thedesired weight of oxyethylene groups was obtained after reaction of thereactive hydrogen compound with ethylene oxide in 3 or 4 stages, theindicated amount of the. intermediate polyoxyethylene polyol was thencharged to the reactor together with KOH as catalyst and TAELEICompositions of Invention- Reeceive Hydrogen Compound. Ethylene Oxidekopylene Oxide Quantities of Reactsnta and Reaction Conditions AmountR50 (or oxyullnylene Amen-pt Ethylene Oxide (E0) Average A'mr g eReactive condensate fi'om previous. Amount Catalyst or Propylene Oxide(P0) Total Reaction Temperature, Pressure, Hydrogen st e Used Grams.(mole) Used. Grams Added Grams SDI-01S! lme. Hours mg Rx. Ccmpound StageStew Stage Stage Stage St g g ifilifilueed A s c n A "B c D A B c .o A Bc D A a c n A u c a l Ethylene +00 ;i sc-' (a) (:1) (a) nonoso- .Po- 52.3 2.0 5.5 105 107 115 1'40 5 7 0 glycol (5A5) 1050 567 690' 28.5 1.9.51 1.0 2 5 1505 1.118 1200 p K (2.35) (0-57) {0.20) (556) (29-?!) (es-133m 2 ntre lene 5'72 A- as- (e) (5) E0- nonoro- 17 22' 21 125 etatatetglycol (6) 100 65 1 i -6 1.2 1 59 879 919 we moawe.

' s: c. a a n e n 0- (a) PO- '2} 120 atmos. 271 1.2 225 (0.08) V ass) 1'hoe 7). sl I no= r'o- Pe- 2. an 1 107 12c 65 6 5 35C3 2 {6.5) 1050 5 315$8 I 22 5a 15:5 553 3 J O5 5 (1-1-5) 6) 1 7 55-5) 9-?) (9- V 7 l maressup A- n- 4.) (a is) 1 EC- 50- m- 75.5 5.5 .5 105108 1 .2 7 ears o 1:0; (6.5) #95 600 35.5 5.0 1.0 2 5 115.- 1200 e 1-1) (0-5) (55-5) 10-1)(av-7) Eiihylene the A acl (s) (A) (a) i at m- 2 5- 2-5 -o 5- 05 10? usM .65 5 8o 75 glycol (6.5) 1030 56-7 W55 7 28.5 3.0.5 1.9 0.5 2 5 15051118 Jil p Because man I (cont-d.)

Amount REC (or oxyalkylene Amount Ethylene Oxide (E) I Average AverageReactive 1 from previous Amount Catalyst or Propylene Oxide (PO) TotalReaction Temperature, Pressure, Hydrogen stge) Used Gran: (mole) UsedGrams Added. Grams (mole) Time, Hours '0. psrig 85:. Compound Sblgc Sta0 St ge St 2 Stage Stage N o; (RHC)UsedABCDABCDABCDABCDABCDABCD 6Ethylene 100 A- a c- (a) (a) (a) (0.) EO-- n0- s0- 20- 5.5 2.5 2.05.01051071151 1865 65 80 78 7 lj-Pemzms 178 A- ac- (c) 1:0- E0- 120- P0-5-5 -5 2.9 6.8 110 155 25 25 -2 5 5 75 (1.56) (0.5 1) (0.25) (11.0)(50.6) (16.05 (2 1.1) 8 Glycerine 160 A- B- (c) 210- 130- 1.9 7.6 5.5125 125125 50 +7 +0 9 Trimsthyl- #00 A- y B- c- (c) s0- E0- PO- 6.9 6.8h.5 1.5125125 155 155 50 70 80 90 olpropane 2.98) +50 1167 61 2 18 182550 1555 507 10 Peirbaeryth- 505 A- s- 0- (a) (c) E0- E0- E0- PO-2.911.6 '..5 7.1125125 125 155 50 9o 85 ritel. 100 900 900 110 12.1 25151160 1780 (129) (0.05) (0.19) (16.0) (52.6) (27.0) (50. v 11 n-Butyl-257 A- s- (e) (0) EO- 20- P0- .1.5 7.1 6.1 60125125 1-2 +0 amine 3.5)580 800 8 20. 1 510 2570 1600 12 Ethylene- 1 11 A- B- c- (e) (c) ro- E0-00- P0- 2.5 6.5 5.6 5.6 95125 125125 2-5 65 55 60 (ii-amine (2) 55k 600700 15.6 552 1860 1560 860 (1-5) M (0.1) 2-5) (5 9) (l 15 1,6-Hexzme-252 A- B- c- (e) (c) (c) EO- EO- 1320- PO- 6.5 18.6 7.8 5.6 155 125 1251-2 95 7o 75 diamine (2) 706 651 90 12.9 5. 552 2181 1555 1505 (1 (0-57)(0.1.1) (8.0) 19- (55.)) (22 9) 1 1 Diethylew 206 A- ac- (e) (c) E0- no-P0- 5.8 7.9 +.5 8.0 90125 1281251-2 65 60 80 trim'ine (1. +1) +00 900800 55 11.9 1 1. 2590 1 6 (1.5) (0. (o 2) (1.1) (5 4.2) (26.1) (27.6) 152-Methyl- 500' A- B- E0- 20- PO- 7.0 9.6 5.8 85 125 125 2 85' 55 pipera-(5.0) L100 70 1 55.5 19 9 26 2270 1008 zine (2-1) (0-6) (6.0) (51-6)(21.5) 16 Acetamide 200 A- B- C- (c) E0- E0- E0- 1=0- 5.810.o 5.8 6. r85 125125125 2 17 B nz n 5 5 A- B- 0- (d) (c) n0- n0- 110- P0- 2.0 6.10. 5 100125125125 2 a 55 15 sulfon- (2.2) 100 800 500 15.5 2220 12501020 amide (1.6) (0.5) (0.2) l .1. 1) (50.5) (28. 1) (18.0)

Note. Catalysts: (0) Sodium hydroxide, (1)) meta Thus, Table 1 abovesummarizes the conditions under which surfactant compositions accordingto the present invention were prepared. These compositions aresummarized in Table II below which reports the reactive hydrogencompound used, the weight percent of the total composition attributableto the oxyethylene groups and the total theoretical molecular weight ofthe oxypropylene chains. Since these compositions were prepared instages, the examples are identified by Example No. and Stage B, C, D,etc. which stand for the preparation of the particular composition. Itwill be noted that two compositions were prepared under Example 2 inTable I, they being represented by Stages D and E in Example 2.

Table II COMPOSITION OF INVENTION Example No. Reactive hydrogen compound09122 2 1 5 5 212 66351 0 g'ency properties bet'ween the compositions ofthe inven- Smge Weight 1 molecular 0 tron and the compositions of theLundsted patent.

Percent Weight The compositions according to the Lundsted patentEthylene glycol 33 3 5,920 were prepared in stages following the samegeneral pro- 2-D 0 22 gig cedure and with the same equipment as thatalready de- 43,1 1: 65 scribed for the compositions of the inventionsummarized 23:2 $18,? in Tables I and II. The significant dilfercncefrom the d. igi r i n e i fi i lm (3 gig rallzthgld :mgioyed in examplesrteicorclllegn Tables I assesses; a; 1222 g gjl f g j j i; W -5 5:15..sense-.1: is @088 3.. mp1... .2... m .athjimfii liii 212.222

3: 8-- ie i' l a ih $1888 accordance with this invention The prepirationof the i335; I 221i compositions of the Lundsted patent is summarizedbel'I-D Benzenesulfonamide 31.8 5,200

low in Table III.

112 sodium, (0) potassium hydroxide, (d) N-methyl morpholine, (a) water.

A parallel series of surfactant compositions according to the Lundstedpatent, US. 2,674,619, was also prepared wherein the reactive hydrogencompound was initially condensed with propylene oxide and the thusproduced poiyoxypropylene polyol was then condensed with ethylene oxide.These compositions were prepared with the proper amount of propyleneoxide and ethylene oxide so that the weight percent oxyethylene groupsand molecular weight of the oxypropylene chains were the same as thesevalues present in many of the compositions according to this inventionsummarized above in Tables I and II. Thus, direct comparisons were thenpossible and were made so as to demonstrate the difference in deter-Table V COMPARISON OF DETERGENOY,

FOAM HEIGHT AND CLOUD POINT PROPERTIES BETWEEN COMPOSI- TIONS OFINVENTION AND COMPOSITIONS OF LUNDSTED PATENT (U.S. 2,674,619)

Composition of Composition of Carbon soil Foam invention Lundsted patentremoval value atheight,

at 120 F. Ex. Reactive hydrogen compound and 400 Cloud N c. Oxyethyl-Oxypropyl- Oxypropyl- Oxyethylml./min. point, 0.

one groups, ene chains, ene chains, ene groups, 90 F. 140 F. flow rate,weight molecular molecular weight mm. percent weight weight percentEthylene glycol 48. 1 1, 024 52 40. Propylene glycol 1, 075 48. 3 134145 79 Ethylene glycol 33 4, 018 284 15 13 Propylene glycol 4, 126 34. 4193 65 44 Ethylene glycol 150 37 17 Propylene glycol 3, 200 49. 5 243600 79 Ethylene glycol 24. 9 8, 955 261 27 7 Propylene glycol 9, 150 24.9 114 42 10 1,5-pentanedi0l 33.0 6, 000 134 152 60 11. 5 d0 6, 000 33.0144 124 70 53. 5 Glycerine 46. 0 4, 000 98 217 30 15. 0 rin 4, 000 46. 0172 183 2 395 74. 3 Trimethylolpropane 66 1 5,000 81 125 0.9 do 5,00066. 1 130 150 1 290 None Pentaerythritol 33 2 9,500 180 192 47 12.5 do9, 500 33. 2 145 117 555 39. 5 32 8 2,500 132 10 17. 5 o 9, 500 33. 2286 280 40 59. 5 Ethylenediamine 44 7 6, 000 162 27 19. 5 do 6, 000 44.7 258 240 71. 0 1,6-hexanediamine 33. 2 12, 000 11. 5 28 o 12, 000 33.2243 123 590 87.0 14 Diethylenetriamiue 33 2 10, 000 206 12.0 29 o 10,000 33. 2 272 143 560 50. 0 15 31 6 2, 500 144 12 19.0 2, 500 31. 6 200285 235 23.0 33 1 6, 000 172 163 11. 0 6, 000 33 1 246 226 47 37. 5 31 85, 200 192 192 35 9. 0 5,200 31 8 218 168 32 38. 5

1 Not determined. 2 Flow rate was 300 nil/min.

It will be apparent from a review of the data recorded in Table V thatthe major objective of this invention has been accomplished. That is,flexibility in the properties of surface active agents based on blockpolymers of propylene oxide and ethylene oxide has been significantlyincreased by our concept of initially condensing ethylene oxide with arelatively low molecular weight reactive hydrogen compound having aplurality of reactive hydrogen atoms and then condensing propylene oxidewith the initially produced polyoxyethylene polyol. The tests made andresults thereof which are recorded in Table V show unmistakably that thecompositions of this invention have distinctly different properties thanthe compositions of the Lundsted patent wherein the relatively lowmolecular weight reactive hydrogen compound is initially condensed withpropylene oxide and the thus produced polyoxypropylene polyol is thencondensed with ethylene oxide. Furthermore, definite trends can be seenupon close re view of the data in Table V. Cloud point is consistentlylower and foam height is consistently lower with the compositions ofthis invention. Detergency as measured by the carbon soil removal testvaries; in some cases the compositions of the invention producedsignificantly higher carbon soil removal values than did thecompositions of the Lundsted patent, e.g., Examples 4, 6, 8 and 10compared to Examples 19, 21, 23 and 25, respectively, While in othercases the compositions of the Lundsted patent produced higher carbonsoil removal values. In any case, an entirely diiierent composition fromthe point of view of chemical and physical properties is producedaccording to the concept of this invention. The comparisons are made, itshould be noted, between pairs of compositions where essentially thesame amounts of the same ingredients were used with sole significantdifference residing in the molecular structure which results from theorder in which propylene oxide and ethylene oxide were used in makingthe compositions.

We claim:

1. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds containing in their structurethe nucleus of a relatively low molecular weight reactive hydrogencompound having from 2 to about 6 reactive hydrogen atoms and having notover 6 carbon atoms per molecule and being selected from the groupconsisting of aliphatic polyhydric alcohols, alkylamines, alkylenepolyamines, cyclicamines, amides, and polycarhoxylic acids, oxyethylenegroups and oxypropylene groups, the structure of the compounds beingsuch that all of the oxyethylene groups are present in polyoxyethylenechains that are attached to the nucleus of the reactive hydrogencompound at the sites of the reactive hydrogen atoms, and all of theoxypropylene groups are present in polyoxypropylene chains that areattached to the polyoxyethylene chains, the average molecular weight ofthe oxypropylene chains being at least about 900 and up to about 25,000,and the oxyethylene groups in the mixture constituting from about 20 toweight percent of the mixture.

2. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds containing in their structurethe nucleus of a relatively low molecular weight reactive hydrogencompound having from 2 to about 6 reactive hydrogen atoms and having notover 6 carbon atoms per molecule and being selected from the groupconsisting of aliphatic polyhydric alcohols, alkylamines, alkylenepolyamines, cyclicamines, amides, and polycarboxylic acids, oxyethylenegroups and oxypropylene groups, the structure of the compounds 'beingsuch that all of the oxyethylene groups are present in polyoxyethylenechains that are attached to the nucleus of the reactive hydrogencompound at the sites of the reactive hydrogen atoms, and all of theoxypropylene groups are present in polyoxypropylene chains that areattached to the polyoxyethylene chains, the average molecular weight ofthe oxypropylene chains being from 1500 to 15,000, and the oxyethylenegroups in the mixture constituting from about 25 to 75 weight percent ofthe mixture.

3. A surface active mixture of conjugated polyoxy- 15 2 wherein saidreactive hydrogen compound is an aliphatic polyhydric alcohol.

4. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds according to claim 2 whereinsaid reactive hydrogen compound is an alkyls amine. V

5. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds according to claim 2 whereinsaid reactive hydrogen compound is an alkylene polyamine.

6. A surface active mixture of conjugated polyoxy- 16ethylene-polyoxypropylene compounds containing in their structure thenucleus of ethylene-diamine, oxyethylene groups and oxypropylene groups,the structure of the compounds being such that all 'of the oxyethylenegroups are present in polyoxyethylene chains that are attached to thenucleus of the ethylene-diamine at the sites of its reactive hydrogenatoms, and all of the oxypropylene groups are present inpolyoxypropylene chains ethylene-polyoxypropylene compounds according toclaim 7 2 wherein said reactive hydrogen compound is an amide.

7. A surface active mixture of conjugatedpolyoxyethylene-ployoxypropylene compounds 7 according to claim 2wherein said reactive hydrogen compound is a polycarboxylic acid.

8. A surface active mixture ofconjugatedpolyoxyethylene-polyoxypropylene compounds containing in theirstructure the nucleus of ethylene glycol, oxyethylene groups andoxypropylene groups, the structure of the compounds being such that allof the oxyethylene groups p are present in polyoxyethylene chains thatare attached to the nucleus of the ethylene glycol at the sites of itsreactive hydrogen atoms, and all of the oxypropylene' groups are presentin polyoxypropylene chains that are attached to the polyoxyethylenechains, the average molecular weight of the oxypropylene chains being atleast about 900 and up to about 25,000, and the oxyethylene groups inthe mixture constituting from about 20 to 90 Weight percent of themixture.

9. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds containing in their structurethe nucleus of propylene glycol, oxyethylene groups and oxypropylenegroups, the structure of the compounds being such that all of theoxyethylene groups are present in'po'lyoxyethylene chains that areattached to the nucleus of the propylene glycol at the sites of itsreactive hydrogen atoms, and all of the oxypropylene groups are presentin polyoxypropylene chains that are attached. to the polyoxyethylenechains, the average molecular weight'of the oxypropylene chaiiisbeing atleast about'900 and up to about 25,000, andthe oxyethylene groups in themixture constitutingfrom'about 20 to 90 weight percent of the mixture.

10. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds containing in their structurethe nucleus otglycerine, oxyethylene groups and'oxypr'opylene groups,the structure of the compounds being such that all of the oxyethylenegroups are present in polyoxyethylene chains that are attached to thenucleus of the glycerine at the sites of its reactive hydrogen atoms,and all of the oxypropylene groups are present in polyoxypropylenechains that are attached to the polyoxyedi'ylenechains, the averagemolecular weight of the oxypropylene chains being at :least about 900and up to about 25,000, and the oxyethylene groups in the mixtureconstituting from about 20 to 90 weight percent of the mixture.

' 11. A surface active mixture of conjugated polyoxythat are attached tothe polyoxyethy-lene chains, the average molecular weight of theoxypropy-lene chains being at least about 900 and up to about 25,000,and the oxyethylene groups in the mixture constituting from about 20 to90 weight percent of the mixture.

12. A surface active mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds containing in their structurethe nucleus of acetamide, oxyethylene groups and oxypropylene groups,the structure of the compounds being such that all of the oxyethylenegroups are present in polyoxyethylene chains that are attached to thenucleus of the acetamide at the sites of its reactive hydrogen atoms,and all of the oxypropylene groups are present in polyoxypropylenechains that are attached to the polyoxyethylene chains, the averagemolecular Weight of the oxypropylene chains being at least about 900 andup to about 25,000, and the oxyethylene groups in the mixture consistingof aliphatic polyhydric alcohols, alkylamines,

alkylene polyamines, cyclicamines, amides, and polycarboxylic acids, toproduce a polyoxyethylene polyol, and subsequently condensing propyleneoxide With said polyoxyethylene polyol, the: amount of propylene oxideused being such that the molecular Weight of the compounds attributableto the propylene oxide is from about 900 to 25,000 and the amount ofethylene oxide used being such that the oxyethylene groups constitutefrom 20 to 90 weight percent of the compounds.

'14. A method in accordance with claim 13 wherein the amount ofpropylene oxide used is such that the molecular Weight of the compoundsattributable to propylene oxide is from 1500 to 15,000.

References ited in the file of this patent De Groote' May 25, 1954

1. A SURFACE ACTIVE MIXTURE OF CONJUGATEDPOLYOXYETHYLENE-POLYOXYPROPYLENE COMPOUNDS CONTAINING IN THEIR STRUCTURETHE NUCLEUS OF A RELATIVELY LOW MOLECULAR WEIGHT REACTIVE HYDROGENCOMPOUND HAVING FROM 2 TO ABOUT 6 REACTIVE HYDROGEN ATOMS AND HAVING NOTOVER 6 CARBON ATOMS PER MOLECULE AND BEING SELECTED FROM THE GROUPCONSISTING OF ALIPHATIC POLYHYDRIC ALCOHOLS, ALKYLAMINES, ALKYLENEPOLYAMINES, CYCLICAMINES, AMIDES, AND POLYCARBOXYLIC ACIDS, OXYETHYLENEGROUPS AND OXYPROPYLENE GROUPS, THE STRUCTURE OF THE COMPOUNDS BEINGSUCH THAT ALL OF THE OXYETHYLENE GROUPS ARE PRESENT IN POLYOXYETHYLENECHAINS THAT ARE ATTACHED TO THE NUCLEUS OF THE REACTIVE HYDROGENCOMPOUND AT THE SITES OF THE REACTIVE HYDROGEN ATOMS, AND ALL OF THEOXYPROPYLENE GROUPS ARE PRESENT IN POLYOXYPROPYLENE CHAINS THAT AREATTACHED TO THE POLYOXYETHYLENE CHAINS, THE AVERAGE MOLECULAR WEIGHT OFTHE OXYPROPYLENE CHAINS BEING AT LEAST ABOUT 900 AND UP TO ABOUT 25,000,AND THE OXYETHYLENE GROUPS IN THE MIXTURE CONSTITUTING FROM ABOUT 20 TO90 WEIGHT PERCENT OF THE MIXTURE.